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Development of new methods for activation of inert N-C bonds
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Shi, Shicheng. Development of new methods for activation of inert N-C bonds. Retrieved from https://doi.org/doi:10.7282/t3-en0v-qe67

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TitleDevelopment of new methods for activation of inert N-C bonds
NameShi, Shicheng (author); Szostak, Michal (chair); Jordan, Frank (internal member); Lalancette, Roger (internal member); Williams, Lawrence (outside member); Rutgers University; Graduate School - Newark
Date Created2019
Other Date2019-10 (degree)
SubjectChemistry, Amide bond activation, Amides -- Electric properties
Extent1 online resource (xvii, 200 pages) : illustrations
DescriptionThe amide bond is one of the most important functional groups in chemistry and biology. It would be appealing to use amides as N-C(O) electrophiles in transition-metal-catalyzed cross-coupling reactions, however, the high activation energy required for N-C(O) scission, a consequence of amidic resonance (approximately 40% double bond character in planar amides, 15-20 kcal/mol barrier to rotation), makes selective metal insertion into the N-C(O) bond a classic problem in catalysis.
In 2015, our group introduced a new mode for amide bond activation enabled through ground-state-destabilization. Based on this concept, we have successfully developed N-acyl-glutarimide amides as highly effective amide-based electrophiles, in which the amide bond exhibits nearly perpendicular twist (T = 87.8ยบ).
This thesis describes our studies on: 1) the development of novel transition-metal-catalyzed transformations of amides by N-C(O) activation; 2) the development of new amide precursors for cross-coupling reactions; 3) the development of new, general catalytic systems for acyl-cross-coupling reactions. Specifically, the thesis addresses: 1) the development of novel decarbonylative cross-coupling reactions using amides as aryl equivalents, including Ni-catalyzed decarbonylative Suzuki cross-coupling, Pd-catalyzed decarbonylative cyanation, and Pd-catalyzed decarbonylative borylation; 2) the development of a general catalytic system for acyl Negishi cross-coupling reactions of N-acyl-glutarimides, N,N-di-Boc2 amides and N-acyl-succinimides; 3) the development of Pd-NHC catalytic systems for acyl Suzuki cross-coupling of esters, acyl Buchwald-Hartwig cross-coupling of amides and esters, and acyl Suzuki cross-coupling of triflamides.
NotePh.D.
NoteIncludes bibliographical references
Genretheses, ETD doctoral
Persistent URLhttps://doi.org/doi:10.7282/t3-en0v-qe67
LanguageEnglish
CollectionGraduate School - Newark Electronic Theses and Dissertations
Organization NameRutgers, The State University of New Jersey
RightsThe author owns the copyright to this work.
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